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  • Bite angle  (1)
  • S ligands  (1)
  • 1
    Electronic Resource
    Electronic Resource
    Subsite-Specific Reactions of a Cyclotriveratrylene [4Fe-4S] Cluster Complex (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1151-1157 
    Details
    ISSN: 0009-2940
    Keywords: Iron-sulfur clusters ; S ligands ; Cyclotriveratrylene ; Subsite-specific reactions ; Electrochemistry ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ligand exchange reactions are carried out exclusively at the unique iron site of a subsite-differentiated cyclotriveratrylene [4Fe-4S] cluster complex. The effect of a variety of thiolate, phenolate, bidentate, and bridging ligands on the redox potential of the subsite-differentiated [4Fe-4S] cluster complex is studied and compared with the effects of such ligands on an [Fe4S4C14]2- cluster. The redox potential can be modulated within the range of -1.60 to -1.80 V (vs. Fc0/+) by varying the ligand. The introduction of an electron releasing substituent shifts the redox potential to more negative values, whereas an electron withdrawing substituent has the opposite effect. A linear relationship exists between the number of substituted sites and the reduction potential of the cluster.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300819
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  • 2
    Electronic Resource
    Electronic Resource
    On the Influence of the Bite Angle of Bidentate Phosphane Ligands on theRegioselectivity in Allylic Alkylation (1999)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1237-1241 
    Details
    ISSN: 1434-1948
    Keywords: Palladium ; Phosphane ligands ; Bite angle ; Allylic alkylation ; Molecular modelling ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The natural bite angle of bidentate phosphane ligands influences the isomer distribution (syn and anti) in (1-methylallyl)(bisphosphane)Pd OTf complexes. It was found (31P- and 1H-NMR studies) that the syn/anti ratio changes from 12 (dppp) to 1.3 (sixantphos). Molecular orbital calculations [PM3(tm) level] indicate that for ligands inducing a large bite angle, the phenyl rings of the ligand embrace the allyl moiety, thus influencing the syn/anti ratio. This bite-angle effect on the syn/anti ratio is transferred to the regioselectivity in stoichiometric allylic alkylation. Ligands inducing large bite angles direct the regioselectivity towards the formation of the branched product 2. Catalytic alkylation of (E)-2-butenyl acetate showed that for ligands with a small bite angle the regioselectivity of the catalytic and stoichiometric alkylation are in good agreement. This correspondence is worse for ligands with a larger bite angle, which is rationalised in terms of the relative rates of syn/anti isomerisation and alkylation. The ligand with the largest bite angle (sixantphos) gives the most active catalytic species.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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